The present invention relates to novel unsymmetric dioxazine dyes which are fibre-reactive, processes for their preparation and their use for dyeing or printing fibre materials.
The practice of dyeing using reactive dyes has recently led to increased requirements regarding the quality of the dyeings and the profitability of the dyeing process. There consequently continues to be a demand for novel reactive dyes which have improved properties, in particular in respect of application.
Reactive dyes which have a high degree of exhaustion and a high degree of fixing, in particular no alkaline after-treatment for removal of unfixed dye being necessary, are nowadays required for dyeing. These dyes should furthermore have a good tinctorial yield and a high reactivity. EP-A-0 260 227 and U.S. Pat. No. 4,841,049 disclose unsymmetric, fibre-reactive dioxazine dyes. However, all the properties of the known dyes do not meet the requirements mentioned.
The present invention is therefore based on the object of providing novel, improved fibre-reactive dioxazine dyes for dyeing and printing fibre materials which have the qualities characterized above to a high degree. The novel dyes should have the distinctive features in particular of high degrees of exhaustion, high fixing yields and high fibre-dye bond stabilities. They should furthermore produce dyeings with good all-round properties, for example light- and wet-fastness properties.
It has been found that the stated object is substantially achieved by the reactive dyes defined below.
The present invention thus provides reactive dyes of the formula (1) 
in which
R1, R2, R3 and R4 independently of one another are hydrogen or substituted or unsubstituted C1-C4alkyl,
(R5)0-2 and (R6)0-2 independently of one another are 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, halogen, carboxyl, sulfo, carbamoyl, N-C1-C4alkylcarbamoyl, N,N-di-C1-C4alkylcarbamoyl, C1-C4alkylsulfonyl, sulfamoyl, N-C1-C4alkylsulfamoyl and N,N-di-C1-C4alkylsulfamoyl,
A is hydrogen or C1-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo, carboxyl or sulfato, phenyl or naphthyl which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, carbamoyl, sulfo or halogen, phenyl-C1-C4alkylene which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, sulfo, carbamoyl, ureido or halogen, or C5-C7cycloalkyl which is unsubstituted or substituted by C1-C4alkyl,
B1 is an aliphatic or aromatic bridge member,
D1 is a radical of the aliphatic, aromatic or heterocyclic series which is substituted by at least one fibre-reactive group,
V1 and V2 independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, or substituted or unsubstituted phenyl, phenoxy, C2-C6alkanoylamino or benzoylamino and X1 is halogen, hydroxyl, C1-C4alkoxy, C1-C4alkylthio, substituted or unsubstituted amino or an N-heterocycle which may contain further heteroatoms, with the proviso that
A and R1 are not hydrogen if B1 is ethylene, 1,3-propylene, 1,4-butylene, phenylene which is unsubstituted or substituted by sulfo, or 1,4-cyclohexylene, or the radical 
xe2x80x83is piperazine and
A is not hydroxyethyl and R1 is not hydrogen if B1 is ethylene and X1 is 2,6-di-sulfophenylamino.
Alkyl radicals R1, R2, R3 and R4 are straight-chain or branched. The alkyl radicals can be further substituted, for example by hydroxyl, sulfo, sulfato, cyano or carboxyl. Examples are the following radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and the corresponding radicals substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred substituents are hydroxyl, sulfo, sulfato or carboxyl, in particular hydroxyl or sulfato. The radical R4 is also a radical of the formula xe2x80x94(CH2)2xe2x80x94SO2xe2x80x94(CH2)2xe2x80x94Cl.
C1-C4alkyl (R5)0-2, (R6)0-2, V1 and V2 independently of one another are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl, and in particular methyl, the definitions and preferences also applying to the following C1-C4alkyl radicals.
C1-C4alkoxy (R5)0-2, (R6)0-2, V1, V2 and X1 independently of one another are, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy and in particular methoxy, the definitions and preferences mentioned also applying to the following C1-C4alkoxy radicals.
C2-C4alkanoylamino (R5)0-2 and (R6)0-2 are, for example, acetylamino or propionylamino, in particular acetylamino, the definitions and preferences mentioned also applying to the following C2-C4alkanoylamino radicals.
Halogen (R5)0-2, (R6)0-2, V1 and V2 independently of one another are, for example, fluorine, chlorine or bromine, preferably chlorine or bromine and in particular chlorine.
N-C1-C4alkylcarbamoyl (R5)0-2 and (R6)0-2 independently of one another are, for example, N-methyl-, N-ethyl-, N-propyl-, N-isopropyl-, N-butyl-, N-sec-butyl-, N-tert-butyl- or N-isobutylcarbamoyl, preferably N-methyl- or N-ethylcarbamoyl and in particular N-methylcarbamoyl.
N,N-di-C1-C4alkylcarbamoyl (R5)0-2 and (R6)0-2 independently of one another are, for example, N,N-di-methyl-, N,N-di-ethyl-, N,N-di-propyl-, N,N-di-isopropyl-, N,N-di-butyl-, N,N-di-sec-butyl- or N,N-di-isobutylcarbamoyl, preferably N,N-di-methyl- or N,N-di-ethylcarbamoyl and in particular N,N-di-methylcarbamoyl.
C1-C4alkylsulfonyl (R5)0-2 and (R6)0-2 independently of one another are, for example, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- or isobutylsulfonyl, preferably methyl- or ethylsulfonyl, and in particular methylsulfonyl.
N-C1-C4alkylsulfamoyl (R5)0-2 and (R6)0-2 independently of one another are, for example, N-methyl-, N-ethyl-, N-propyl-, N-isopropyl-, N-butyl-, N-sec-butyl-, N-tert-butyl- or N-isobutylsulfamoyl, preferably N-methyl- or N-ethylsulfamoyl and in particular N-methylsulfamoyl.
N,N-di-C1-C4alkylsulfamoyl (R5)0-2 and (R6)0-2 independently of one another are, for example, N,N-di-methyl-, N,N-di-ethyl-, N,N-di-propyl-, N,N-di-isopropyl-, N,N-di-butyl-, N,N-di-sec-butyl- or N,N-di-isobutylsulfamoyl, preferably N,N-di-methyl- or N,N-di-ethylsulfamoyl and in particular N,N-di-methylsulfamoyl.
In a preferred embodiment of the reactive dyes according to the invention, A is C1-C4alkyl, which is unsubstituted or substituted by hydroxyl, sulfo, carboxyl or sulfato, phenyl or naphthyl which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, carbamoyl, sulfo or halogen, in particular phenyl which is unsubstituted or substituted by the radicals mentioned, phenyl-C1-C4alkylene which is unsubstituted or substituted in the phenyl ring by C1-C4-alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, sulfo, carbamoyl, ureido or halogen, or C5-C7-cycloalkyl which is unsubstituted or substituted by C1-C4alkyl.
A in the reactive dyes according to the invention is particularly preferably C1-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo, carboxyl or sulfato, preferably hydroxyl or sulfato, and in particular sulfato. The substituted alkyl radicals are preferred.
An aliphatic bridge member B1 is, for example, a C2-C12alkylene radical, in particular a C2-C6alkylene radical, which can be interrupted by 1, 2 or 3 members from the group consisting of xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 and, in particular, xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred substituents of the alkylene radicals B1 are hydroxyl, sulfo or sulfato, in particular hydroxyl or sulfato.
Aliphatic bridge members B1 are furthermore, for example, C5-C9-cycloalkylene radicals, in particular cyclohexylene radicals. The cycloalkylene radicals mentioned can be unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl, in particular by C1-C4alkyl. Aliphatic bridge members B1 are furthermore methylenecyclohexylene, ethylenecyclohexylene or methylenecyclohexylenemethylene radicals which are unsubstituted or substituted in the cyclohexylene ring by C1-C4alkyl, in particular methyl.
The radical of the formula 
is, for example, also a radical of the formula 
in which alk is C1-C4alkylene, for example ethylene.
An aromatic bridge member B1 is, for example, C1-C6alkylphenylene, for example methylenephenylene, C1-C4alkylenephenylen-C1-C4alkylene, for example methylenephenylenemethylene, or phenylene which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl, or a radical of the formula 
in which the benzene rings I and II are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl and L is the direct bond or a C2-C10alkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Nxe2x95x90Nxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94SO2xe2x80x94 xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94SO2xe2x80x94. An aromatic bridge member B1 is preferably phenylene, which can be substituted as defined above. Preferably, the aromatic bridge members B1 are unsubstituted or substituted by sulfo.
B1 is preferably a C2-C12alkylene radical, which can be interrupted by 1, 2 or 3 members from the group consisting of xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 or xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl;
a C5-C9-cycloalkylene radical, C1-C6alkylenephenylene radical or phenylene radical which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl; or the radical of the formula 
xe2x80x83is a radical of the formula 
B1 is particularly preferably a C2-C12alkylene radical, which can be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl, or
a phenylene radical which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl.
B1 is especially preferably a C2-C12alkylene radical, in particular a C2-C6alkylene radical, for example 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,5-pentylene, 3,5-pentylene, 1,6-hexylene, 2,5-hexylene, 4,6-hexylene or the radicals of the formula 
xe2x80x83which can be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl or sulfato, and is preferably not interrupted by xe2x80x94Oxe2x80x94.
Especially important bridge members B1 are those of the formula xe2x80x94CH2xe2x80x94CH(R7)xe2x80x94 or xe2x80x94(R7)CHxe2x80x94CH2xe2x80x94, in which R7 is C1-C4alkyl, in particular methyl.
Fibre-reactive radicals contained in the radical D1 are to be understood as meaning those which are capable of reacting with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and thiol groups in wool and silk, or the amino and any carboxyl groups of synthetic polyamides to form covalent chemical bonds. The fibre-reactive radicals are as a rule bonded to the dye radical directly or via a bridge member. Suitable fibre-reactive radicals are, for example, those which contain at least one substituent which can be split off from an aliphatic, aromatic or heterocyclic radical, or in which the radicals mentioned contain a radical which is capable of reaction with the fibre material, for example a vinyl radical.
Preferred fibre-reactive radicals D1 are the radicals of the formula (2a), (2b), (2c), (2d), (2e), (2f) or (2g)
xe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2a),
xe2x80x94NHxe2x80x94COxe2x80x94(CH2)lxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2b),
xe2x80x94CONR8xe2x80x94(CH2)mxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2c),
xe2x80x94NHxe2x80x94COxe2x80x94CH(hal)xe2x80x94CH2xe2x80x94halxe2x80x83xe2x80x83(2d),
xe2x80x94NHxe2x80x94COxe2x80x94C(hal)xe2x95x90CH2xe2x80x83xe2x80x83(2e), 
in which
hal is chlorine or bromine;
X2 is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;
T1 independently has the meaning of X2, is a substituent which is not fibre-reactive or is a fibre-reactive radical of the formula (3a), (3b), (3c), (3d), (3e) or (3f) 
xe2x80x83in which
R8 and R10 independently of one another are each hydrogen, C1-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxyl or cyano or a radical 
R9 and R12 independently of one another are each hydrogen or C1-C4alkyl,
R11 is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C1-C4alkoxycarbonyl, C1-C4alkanoyloxy, carbamoyl or the group xe2x80x94SO2xe2x80x94Y,
alk and alk1 independently of one another are linear or branched C1-C6alkylene, arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxyl, C1-C4alkyl, C1-C4alkoxy or halogen,
Q is a radical xe2x80x94Oxe2x80x94 or xe2x80x94NR12xe2x80x94, in which R12 is as defined above,
W is a group xe2x80x94SO2xe2x80x94NR8xe2x80x94, xe2x80x94CONR8xe2x80x94 or xe2x80x94NR8COxe2x80x94, in which R8 is as defined above,
Y is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U and U is a group which can be split off under alkaline conditions,
Y1 is a group xe2x80x94CH(hal)xe2x80x94CH2xe2x80x94hal or xe2x80x94C(hal)xe2x95x90CH2 and hal is chlorine or bromine and
l and m independently of one another are an integer from 1 to 6 and n is the number 0 or 1; and
X3 is halogen or C1-C4alkylsulfonyl;
X4 is halogen or C1-C4alkyl and
T2 is hydrogen, cyano or halogen.
A group U which can be split off under alkaline conditions is, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OPO3H2, xe2x80x94OCOxe2x80x94C6H5, xe2x80x94OSO2xe2x80x94C1-C4alkyl or xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. U is preferably a group of the formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, in particular xe2x80x94Cl or xe2x80x94OSO3H and particularly preferably xe2x80x94OSO3H.
Examples of suitable radicals Y are accordingly vinyl, xcex2-bromo- or xcex2-chloroethyl, xcex2-acetoxyethyl, xcex2-benzoyloxyethyl, xcex2-phosphatoethyl, xcex2-sulfatoethyl and xcex2-thiosulfatoethyl. Y is preferably vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl and in particular vinyl or xcex2-sulfatoethyl.
R8 and R10 independently of one another are preferably hydrogen or C1-C4alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and particularly preferably hydrogen, methyl or ethyl. R8 and R10 are particularly preferably hydrogen.
R9 and R12 independently of one another are each preferably hydrogen, methyl or ethyl, and particularly preferably hydrogen.
R11 is preferably hydrogen.
l and m independently of one another are preferably the number 2, 3 or 4, and particularly preferably the number 2 or 3.
Especially preferably, l is the number 3 and m is the number 2.
A non-reactive substituent T1 can be, for example, hydroxyl; C1-C4alkoxy; C1-C4alkylthio which is unsubstituted or substituted by hydroxyl, carboxyl or sulfo; amino; amino which is mono- or disubstituted by C1-C8alkyl, where the alkyl is unsubstituted or further substituted, for example by sulfo, sulfato, hydroxyl, carboxyl or phenyl, in particular by sulfo or hydroxyl, and is uninterrupted or interrupted by a radical xe2x80x94Oxe2x80x94; cyclohexylamino; morpholino; N-C1-C4alkyl-N-phenylamino or phenylamino or naphthylamino, where the phenyl or naphthyl is unsubstituted or substituted, for example by C1-C4alkyl, C1-C4alkoxy, carboxyl, sulfo or halogen.
Examples of suitable non-reactive substituents T1 are amino, methylamino, ethylamino, xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, xcex2-sulfoethylamino, cyclohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or isopropoxy and hydroxyl.
A radical T1 which is not fibre-reactive is preferably C1-C4alkoxy, C1-C4alkylthio which is unsubstituted or substituted by hydroxyl, carboxyl or sulfo, hydroxyl, amino, N-mono- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl part by hydroxyl, sulfato or sulfo, morpholino, phenylamino or N-C1-C4alkyl-N-phenylamino, which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, chlorine, acetylamino, methyl or methoxy and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups.
Particularly preferred radicals T1 which are not fibre-reactive are amino, N-methylamino, N-ethylamino, morpholino, phenylamino, 2-, 3- or 4-sulfophenylamino or N-C1-C4alkyl-N-phenylamino.
Halogen X2 is, for example, fluorine, chlorine or bromine, and in particular chlorine or fluorine.
Halogen T2, X3 and X4 are, for example, fluorine, chlorine or bromine, in particular chlorine or fluorine.
C1-C4alkylsulfonyl X3 is, for example, ethylsulfonyl or methylsulfonyl, and in particular methylsulfonyl.
C1-C4alkyl X4 is, for example, methyl , ethyl, n- or isopropyl, n-, iso or tert-butyl and in particular methyl.
X3 and X4 are preferably independently of one another chlorine or fluorine.
T2 is preferably cyano or chlorine.
Hal is preferably bromine.
Alk and alk1 independently of one another are, for example, a methylene-, ethylene-, 1,3-propylene-, 1,4-butylene-, 1,5-pentylene- or 1,6-hexylene radical or branched isomers thereof.
Preferably, alk and alk1 independently of one another are each a C1-C4alkylene radical, and particularly preferably an ethylene radical or propylene radical.
Arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or substituted, for example, by sulfo, methyl, methoxy or carboxyl, and particularly preferably an unsubstituted 1,3- or 1,4-phenylene radical.
Q is preferably xe2x80x94NHxe2x80x94 or xe2x80x94Oxe2x80x94, and particularly preferably xe2x80x94Oxe2x80x94.
W is preferably a group of the formula xe2x80x94CONHxe2x80x94 or xe2x80x94NHCOxe2x80x94, in particular a group of the formula xe2x80x94CONHxe2x80x94.
n is preferably the number 0.
The reactive radicals of the formulae (3a) to (3f) are preferably those in which W is a group of the formula xe2x80x94CONHxe2x80x94, R10, R11 and R12 are each hydrogen, Q is the radical xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94, alk and alk1 independently of one another are each ethylene or propylene, arylene is phenylene which is unsubstituted or substituted by methyl, methoxy, carboxyl or sulfo, Y is vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl, Y1 is xe2x80x94CHBrxe2x80x94CH2Br or xe2x80x94CBrxe2x95x90CH2 and n is the number 0.
Fibre-reactive radicals D1 are particularly preferably radicals of the formula (2a), (2c), (2d), (2e) or (2f) in which Y is vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl, hal is bromine, R8 and R9 are hydrogen, m is the number 2 or 3, X2 is chlorine or fluorine, T1 is C1-C4alkoxy, C1-C4alkylthio, which is unsubstituted or substituted by hydroxyl, carboxyl or sulfo, hydroxyl, amino, N-mono or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino or N-C1-C4alkyl-N-phenylamino, which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, chlorine, acetylamino, methyl or methoxy and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups, or a fibre-reactive radical of the formula (3axe2x80x2), (3bxe2x80x2), (3cxe2x80x2), (3dxe2x80x2) or (3fxe2x80x2) 
in particular (3cxe2x80x2) or (3dxe2x80x2), in which
Y is as defined above and
Y1 is a group xe2x80x94CH(Br)xe2x80x94CH2xe2x80x94Br or xe2x80x94C(Br)xe2x95x90CH2.
In the case of the radicals of the formulae (3axe2x80x2) and (3bxe2x80x2), Y is preferably xcex2-chloroethyl. In the case of the radicals of the formulae (3cxe2x80x2) and (3dxe2x80x2), Y is preferably vinyl or xcex2-sulfatoethyl.
A radical D1 of the aliphatic series is, for example, a radical of the formula
xe2x80x94(CH2)2xe2x80x94SO2xe2x80x94(CH2)2xe2x80x94Cl or xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94SO2xe2x80x94(CH2)2xe2x80x94Cl.
Radicals D1 of the aromatic series are, for example, radicals of the benzene or naphthalene series.
Radicals D1 of the benzene or naphthalene series are, for example, phenyl or naphthyl which are unsubstituted or further substituted by substituents which are not fibre-reactive. Substituents which are not fibre-reactive are, for example, C1-C4alkyl, which is to be understood as meaning methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl; C1-C4alkoxy, which is to be understood as meaning methoxy, methoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy; hydroxyl-C1-C4alkoxy; phenoxy; C2-C6alkanoylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy, for example acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino; benzoylamino which is unsubstituted or substituted in the phenyl moiety by hydroxyl, sulfo, halogen, C1-C4alkyl or C1-C4alkoxy; C1-C6alkoxycarbonylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, C1-C4alkyl or C1-C4alkoxy; phenoxycarbonylamino which is unsubstituted or substituted in the phenyl moiety by hydroxyl, C1-C4alkyl or C1-C4alkoxy; amino; N-C1-C4alkyl- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by hydroxyl, C1-C4alkoxy, carboxyl, cyano, halogen, sulfo, sulfato, phenyl or sulfophenyl, for example methylamino, ethylamino, N,N-dimethylamino, N,N-diethylamino, xcex2-cyanoethylamino, xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, xcex2-sulfoethylamino, xcex3-sulfo-n-propylamino, xcex2-sulfatoethylamino, N-ethyl-N-(3-sulfobenzyl)-amino, or N-(xcex2-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino or N-C1-C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl moiety by nitro, C1-C4alkyl, C1-C4alkoxy, carboxyl, halogen or sulfo; C1-C4alkoxycarbonyl, for example methoxy- or ethoxycarbonyl; trifluoromethyl; nitro; cyano; halogen, which is to be understood generally as meaning, for example, fluorine, bromine or, in particular, chlorine; ureido; hydroxyl; carboxyl; sulfo; sulfomethyl; carbamoyl; carbamido; sulfamoyl; N-phenylsulfamoyl or N-C1-C4alkyl-N-phenylsulfamoyl which are unsubstituted or substituted in the phenyl moiety by sulfo or carboxyl; and C1-C4alkylsulfonyl, for example, methyl- or ethylsulfonyl.
Radicals D1 of the benzene, naphthalene or heterocyclic series are furthermore, for example, mono- or disazo radicals of the formula (4) or (5)
D*xe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)uxe2x80x94Kxe2x80x94xe2x80x83xe2x80x83(4)
or
xe2x80x94D*xe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)uxe2x80x94Kxe2x80x83xe2x80x83(5),
in which
D* is the radical of a diazo component of the benzene or naphthalene series,
M is the radical of a middle component of the benzene or naphthalene series,
K is the radical of a coupling component of the bezene, naphthalene, pyrazolone,
6-hydroxypyrid-2-one or acetoacetic acid amide series,
and u is the number 0 or 1, preferably 0, where D*, M and K can furthermore carry substituents customary in azo dyes, for example the substituents mentioned above for phenyl or naphthyl D1 which are not fibre-reactive, and preferably C1-C4alkyl or C1-C4alkoxy, which are unsubstituted or further substituted by hydroxyl, sulfo or sulfato, halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C2-C4alkanoylamino, C1-C4alkylsulfonylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or sulfo or phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo.
Preferred mono- or disazo radicals D1 of the formula (4) or (5) are the radicals of the formula (6a), (6b), (6c), (6d), (6e), (6f), (6g), (6h), (6i), (6j), (6k), (6l), (6m), (6n), or (6o) 
in which (R13)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo and Z1 is a radical of the formula (2a), (2b), (2c), (2d), (2e), (2f) or (2g), where the radicals of the formulae (2a), (2b), (2c), (2d), (2e), (2f) and (2g) are as defined and preferred above, 
in which (R13)0-2 is as defined above, 
in which (R14)0-4 is 0 to 4 identical or different substituents from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, amino, C2-C4alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C1-C4alkylsulfonylamino and sulfo and Z1 is as defined above, 
in which Z1 is as defined above and Z2 is a radical of the formula (2b), (2d), (2e), (2f) or (2g), where the radicals of the formulae (2b), (2d), (2e), (2f) and (2g) are as defined and preferred above, 
in which Z2 is as defined above, 
in which (R13)0-2 is as defined above, (R15)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo and Z1 is as defined above, 
in which B2 is substituted or unsubstituted C2-C6alkylene, R16 is hydrogen, C1-C4alkyl or phenyl, and R17 is hydrogen, cyano, carbamoyl or sulfomethyl, and Z2 is as defined above, 
in which
(R13)0-2, (R14)0-3, (R15)0-3 and Z1 are each as defined above and (R13xe2x80x2)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo.
The numbers on the naphthyl rings of the radicals of the formula (6a), (6b), (6c), (6d), (6f), (6g) or (6h) identify the possible bonding positions of the corresponding substituents.
C1-C4alkylsulfonylamino (R14)0-4 is, for example, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- or isobutylsulfonylamino, preferably methyl- or ethylsulfonylamino, and in particular methylsulfonylamino.
C2-C6alkylene B2 are straight-chain or branched alkylene groups, for example 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,5-pentylene, 3,5-pentylene, 1,6-hexylene, 2,5-hexylene, 4,6-hexylene or the radicals of the formula 
The radicals B2 mentioned are unsubstituted or substituted, for example by hydroxyl, sulfo, carboxyl or sulfato, preferably hydroxyl or sulfato, and in particular sulfato, and are preferably unsubstituted.
B2 is preferably C2-C4alkylene, in particular 1,2-ethylene.
A particularly preferred mono- or disazo radical D1 is the radical of the formula (6j), in which B2, R16, R17 and Z2 are as defined and preferred above.
In a particular embodiment of the present invention, a radical D1 of the benzene, naphthalene or heterocyclic series is a mono- or disazo radical of the formula (4) or (5), where the radicals of the formula (4) or (5) are as defined or preferred above.
In a preferred embodiment of the reactive dyes according to the invention, D1 is a radical of the formula (7) or (6jxe2x80x2) 
in which
(R18)0-3 is 0 to 3 identical or different substituents chosen from the group consisting of halogen, C1-C4alkyl, C1-C4alkoxy, carboxyl, nitro and sulfo and
Z is a radical of the formula (2a), (2c), (2d), (2e) or (2f), in which
R8 and R9 are hydrogen,
hal is bromine,
Y is vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl,
T1 is C1-C4alkoxy, C1-C4alkylthio which is unsubstituted or substituted by hydroxyl, carboxyl or sulfo, hydroxyl, amino, N-mono- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino or N-C1-C4alkyl-N-phenylamino, which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, chlorine, acetylamino, methyl or methoxy and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups, or a fibre-reactive radical of the formula (3cxe2x80x2) or (3dxe2x80x2) 
and Y is as defined above,
X2 is chlorine or fluorine and
m is the number 2 or 3, in particular 2; or 
xe2x80x83in which
B2 is C2-C6alkylene which is unsubstituted or substituted by hydroxyl, sulfo, carboxyl or sulfato, preferably hydroxyl or sulfato,
D2 is a radical of the formula (7) in which (R18)0-3 is as defined above and Z is a radical of the formula (2a), (2c), (2d) or (2e), in particular (2a), in which R8, hal, Y and m are as defined above,
R16 is hydrogen, C1-C4alkyl or phenyl,
R17 is hydrogen, cyano, carbamoyl or sulfomethyl,
R19 is hydrogen, methyl or ethyl, in particular hydrogen, and
R9 and X2 are as defined above.
In a particularly preferred embodiment of the reactive dyes according to the invention, D1 is a radical of the formula (7a), (7b), (7c), (7d) or (6jxe2x80x3) 
in which
(R18)0-2 is 0 to 2 identical or different substituents chosen from the group consisting of halogen, C1-C4alkyl, C1-C4alkoxy and sulfo, in particular methyl, methoxy and sulfo,
Y is vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl, in particular vinyl or xcex2-sulfatoethyl,
Y1 is a group xe2x80x94CH(Br)xe2x80x94CH2xe2x80x94Br or xe2x80x94C(Br)xe2x95x90CH2 and
m is the number 2 or 3, in particular 2; or 
xe2x80x83in which
B2 is C2-C4alkylene, in particular ethylene,
D2 is a radical of the formula (7a), (7b), (7c) or (7d), in particular (7a), in which
(R18)0-2, Y, Y1 and m are as defined and preferred above,
R16 is methyl or ethyl, in particular methyl,
R17 is carbamoyl or sulfomethyl, in particular carbamoyl, and
X2 is fluorine or chlorine.
In an especially preferred embodiment of the reactive dyes according to the invention, D1 is a radical of the formula (7a), (7b), (7c) or (6jxe2x80x3), in particular (7a), (7b) or (6jxe2x80x3), in which (R18)0-2, Y, m, B2, D2, R16, R17 and X2 are as defined and preferred above.
Phenyl V1 and V2 independently of one another are unsubstituted or substituted, for example by C1-C4alkyl, for example methyl or ethyl; C1-C4alkoxy, for example methoxy or ethoxy; C2-C4alkanoylamino; for example acetylamino or propionylamino; carboxyl; carbamoyl; sulfo or halogen, for example chlorine or bromine.
Phenoxy V1 and V2 independently of one another are unsubstituted or substituted in the phenyl ring, for example by C1-C4alkyl, for example methyl or ethyl; C1-C4alkoxy, for example methoxy or ethoxy, C2-C4alkanoylamino; for example acetylamino or propionylamino; carboxyl; carbamoyl; sulfo or halogen, for example chlorine or bromine.
C2-C6alkanoylamino, in particular C2-C4alkanoylamino, V1 and V2 independently of one another are unsubstituted or substituted in the alkyl moiety, for example by sulfo, sulfato, carboxyl, hydroxyl or C1-C4alkoxy, for example methoxy or ethoxy. Examples are acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino, in particular acetylamino.
Benzoylamino V1 and V2 independently of one another are unsubstituted or substituted in the phenyl moiety, for example by hydroxyl; sulfo; carboxyl; carbamoyl; halogen, for example chlorine or bromine; C1-C4alkyl, for example methyl or ethyl; or C1-C4alkoxy, for example methoxy or ethoxy.
V1 and V2 are preferably chlorine, bromine, acetylamine or propionylamino, and in particular chlorine.
V1 and V2 are identical or non-identical, preferably identical.
Halogen X1 is, for example, fluorine, chlorine or bromine, and in particular chlorine or fluorine.
C1-C4alkylthio X1 is, for example, methylthio, ethylthio, n-propylthio, isopropylthio or n-butylthio, in particular ethylthio or n-propylthio. The radicals mentioned are unsubstituted or substituted in the alkyl moiety by hydroxyl, carboxyl or sulfo. The substituted radicals are preferred.
Substituted or unsubstituted amino X1 is amino which is unsubstituted or substituted on the N-atom, for example the following radicals:
N-mono- or N,N-di-C1-C4alkylamino, which includes both the unsubstituted radicals and the radicals substituted in the alkyl moiety, for example by C1-C4alkoxy, hydroxyl, sulfo or sulfato; the radicals substituted in the alkyl moiety are preferred;
C5-C7cycloalkylamino, which includes both the unsubstituted radicals and the radicals substituted in the cycloalkyl ring, for example by C1-C4alkyl, in particular methyl; the corresponding cyclohexyl radicals are preferred as such radicals;
phenylamino or N-C1-C4alkyl-N-phenylamino, which includes both the unsubstituted radicals and the radicals substituted in the phenyl ring, for example C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo; these radicals are preferably unsubstituted in the phenyl ring or substituted by sulfo.
An N-heterocycle X1 which may contain further heteroatoms is, for example, morpholino or piperidin-1-yl.
X1 is preferably fluorine or chlorine.
R1, R2, R3 and R4 preferably independently of one another are hydrogen or C1-C4alkyl and in particular hydrogen.
R5 and R6 are preferably hydrogen.
Preferably, the reactive dyes according to the invention have the formula (1a) 
in which A, B1, D1 and X1 are as defined and preferred above.
Particularly preferably, the reactive dyes of the formula (1a) according to the invention are those in which
A is C1-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo, carboxyl or sulfato, phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, carbamoyl, sulfo or halogen, phenyl-C1-C4alkylene which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, sulfo, carbamoyl, ureido or halogen or C5-C7cycloalkyl which is unsubstituted or substituted by C1-C4alkyl, and preferably C1-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo, carboxyl or sulfato;
B1 is a C2-C12alkylene radical, which can be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl, or phenylene which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl, preferably a C2-C12alkylene radical, in particular a C2-C6alkylene radical, which can be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl or sulfato, and especially preferably a radical of the formula xe2x80x94CH2xe2x80x94CH(R7)xe2x80x94 or xe2x80x94(R7)CHxe2x80x94CH2xe2x80x94, in which R7 is C1-C4alkyl;
X1 is fluorine or chlorine; and
D1 is a radical of the formula (7) or (6jxe2x80x2), in which (R18)0-3, Z, B2, D2, R9, R16, R17, R19 and
X2 are as defined and preferred above, in particular has the formula (7a), (7b), (7c), (7d) or (6jxe2x80x3), in which (R18)0-2, Y, Y1, m, B2, D2, R16, R17 and X2 are as defined and preferred above.
Especially preferably, the reactive dyes of the formula (Ia) according to the invention are those in which
A is C1-C4alkyl substituted by hydroxyl or sulfato,
B1 is a radical of the formula xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94 or xe2x80x94(CH3)CHxe2x80x94CH2xe2x80x94,
X1 is fluorine or chlorine,
D1 is a radical of the formula (7a), (7b), (7c) or (6jxe2x80x3), in particular (7a), (7b) or (6jxe2x80x3), in which (R18)0-2, Y, m, B2, D2, R16, R17 and X2 are as defined and preferred above.
The present invention also relates to a process for the preparation of the reactive dyes according to the invention, which comprises reacting a compound of the formula (8) 
with a compound of the formula (9) 
to give a compound of the formula (10) 
reacting the compound of the formula (10) with a compound of the formula (11) 
to give a compound of the formula (12) 
cyclizing the compound of the formula (12) to give a compound of the formula (13) 
and subjecting the compound of the formula (13) to a condensation reaction in any desired sequence with 2,4,6-trihalogeno-s-triazine and a compound of the formula (14) 
to give a compound of the formula (15) 
in which R1, R2, R3, R4, (R5)0-2, (R6)0-2, A, B1, D1, V1 and V2 are as defined above, Rxe2x80x2 is C1-C4alkyl, V is chorine or bromine, in particular chlorine, and X is halogen, and in particular fluorine or chlorine.
The halogen atom X in the compound of the formula (15) can be replaced by subjecting the compound of the formula (15) to a condensation reaction with a compound of the formula (16)
X1xe2x80x94Hxe2x80x83xe2x80x83(16),
in which X1 is as defined above, with the exception of halogen.
Condensation reactions of dyes containing amino groups with 2,4,6-trihalogeno-s-triazine are known and are described, for example, in EP-A-0 260 227 and U.S. Pat. No. 4,841,049.
The compounds of the formula (8), (9), (11) and (14) are known or can be obtained in a manner known per se.
If appropriate, the end product can also be subjected to a conversion reaction. Such a conversion reaction is, for example, the conversion of a vinylatable reactive group contained in D1 into its vinyl form by treatment with dilute sodium hydroxide solution, for example the conversion of the xcex2-sulfatoethylsulfonyl or xcex2-chloroethylsulfonyl group into the vinylsulfonyl radical. Such reactions are known per se.
The compounds of the formula (1) according to the invention are suitable as dyes for dyeing and printing widely varying materials, such as fibre materials containing hydroxyl groups or containing nitrogen. Examples of nitrogen-containing fibre materials are silk, leather, wool, polyamide fibres and polyurethanes. The dyes according to the invention are particularly suitable for dyeing and printing all types of cellulosic fibre materials. Such cellulosic fibre materials are, for example, the natural cellulose fibres, such as cotton, linen and hemp, as well as pulp and regenerated cellulose, preferably cotton. The dyes according to the invention are also suitable for dyeing or printing cellulosic blend fabrics, for example mixtures of cotton and polyamide fibres or, in particular, cotton/polyester blends.
The dyes according to the invention can be applied to the fibre material and fixed on the fibre in various ways, in particular in the form of aqueous dye solutions and printing pastes. They are suitable both for the exhaust method and for dyeing by the pad-dyeing method, in which the goods are impregnated with aqueous dye solutions, which may contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate under the action of heat or by storage at room temperature for several hours. After the fixing, the dyeings or prints are rinsed thoroughly with cold and hot water, if appropriate with the addition of an agent which has a dispersing action and promotes diffusion of the non-fixed portions.
The dyes according to the invention are distinguished by a high reactivity, good fixing capacity and a very good build-up capacity. They can therefore be used by the exhaust dyeing method at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and the non-fixed portions can easily be washed out, the difference between the degree of exhaustion and the degree of fixing being remarkably small, i.e. the soaping loss is very low. The dyes according to the invention are also particularly suitable for printing, in particular on cotton, but likewise also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics which contain wool or silk.
The dyeings and prints produced with the dyes according to the invention have a high colour strength and a high fibre-dye bond stability both in the acid and in the alkaline range, and furthermore good light fastness properties and very good wet fastness properties, such as fastnesses to washing, water, seawater, cross dyeing and perspiration, as well as a good fastness to pleating, fastness to ironing and fastness to rubbing.
The following examples serve to illustrate the invention. Temperatures are in degrees Celsius, parts are parts by weight and the percentage data are percentages by weight, unless noted otherwise. Parts by weight bear the same relation to parts by volume as the kilogram to the litre.